bis(2,2,2-trifluoroethyl) 2-benzylmalonate | 478074-23-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: bis(2,2,2-trifluoroethyl) 2-benzylmalonate
• 英文别名: Bis(2,2,2-trifluoroethyl) 2-benzylpropanedioate
• CAS: 478074-23-6
• 化学式: C₁₄H₁₂F₆O₄
• 分子量: 358.237
• InChiKey: VIBIEYGUHXXWGD-UHFFFAOYSA-N

物化性质

• 沸点：
  305.9±42.0 °C(Predicted)
• 密度：
  1.370±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  bis(2,2,2-trifluoroethyl) 2-benzylmalonate 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 56.75h， 生成 bis(2,2,2-trifluoroethyl) 2-benzyl-2-(3-(naphthalen-1-yl)prop-2-yn-1-yl)malonate
  参考文献：
  名称：

  1,4-铑（i）迁移，铑催化丙二酸炔基酯的芳基环化†

  摘要：

  描述了通过铑（I）催化的丙二酸炔基酯与芳基硼酸的反应合成官能化的1-四氢萘酮。这些芳基环化是通过烯基至芳基的1，4-Rh（I）迁移进行的，这是关键步骤。还提供了这些反应的对映选择性变体的初步结果。

  DOI：

  10.1039/c9cc05205d
• 作为产物：
  描述：

  2,2,2-三氟乙醇 、 苄基丙二酸 在 二乙胺基三氟化硫 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以73%的产率得到bis(2,2,2-trifluoroethyl) 2-benzylmalonate
  参考文献：
  名称：

  XtalFluor-E介导的全氟化醇直接酯化羧酸

  摘要：

  据报道，由XtalFluor-E介导的羧酸与全氟化醇直接酯化。仅使用稍微过量的（2当量）全氟化醇，就可以以中等到极高的收率，用宽范围的羧酸（包括芳族，杂芳族，脂族和非外消旋手性底物）获得相应的多氟化酯。对照实验表明，该反应不通过的酰基氟化物的形成继续进行，但最有可能通过一个（二乙基氨基）二氟- λ 4硫烷基羧酸盐中间体。

  DOI：

  10.1021/acs.orglett.6b03365

文献信息

• Enantioselective Synthesis of Chiral Cyclopent-2-enones by Nickel-Catalyzed Desymmetrization of Malonate Esters
  作者：Somnath Narayan Karad、Heena Panchal、Christopher Clarke、William Lewis、Hon Wai Lam

  DOI：10.1002/anie.201805578

  日期：2018.7.16

  enantioselective synthesis of highly functionalized chiral cyclopent-2-enones by the reaction of alkynyl malonate esters with arylboronic acids is described. These desymmetrizing arylative cyclizations are catalyzed by a chiral phosphinooxazoline/nickel complex, and cyclization is enabled by the reversible E/Z isomerization of alkenylnickel species. The general methodology is also applicable to the synthesis of

  描述了通过丙二酸炔基酯与芳基硼酸的反应的高官能化手性环戊-2-烯酮的对映选择性合成。通过手性膦基恶唑啉/镍络合物催化这些脱对称芳基环化反应，并且通过烯基镍物质的可逆E / Z异构化作用实现环化反应。通用方法也适用于1,6-二氢吡啶3-3（2H）-one的合成。
• Azodicarbonyl dimorpholide (ADDM): an effective, versatile, and water-soluble Mitsunobu reagent
  作者：Maryanna E. Lanning、Steven Fletcher

  DOI：10.1016/j.tetlet.2013.06.049

  日期：2013.8

  One of the caveats of the Mitsunobu reaction is the often difficult and laborious purification of the reaction mixture. Herein, we show that azodicarbonyl dimorpholide (ADDM) is an effective and versatile Mitsunobu reagent, which, along with its reduced form ADDM-H-2, may be removed from the reaction mixture by a simple aqueous extraction. Furthermore, we demonstrate that the isolated ADDM-H-2 may be re-oxidized with silver(I) oxide to regenerate ADDM. Finally, a chromatography-free Mitsunobu reaction is presented. (C) 2013 Elsevier Ltd. All rights reserved.
• Palladium-catalyzed regiocontrolled and stereoselective alkylations of bis(trifluoroethyl) malonates with dienyl alcohols
  作者：James M. Takacs、Xun-tian Jiang、Alexei P. Leonov

  DOI：10.1016/s1268-7731(03)00074-2

  日期：2003.9

  The triethylborane-promoted and palladium-catalyzed reactions of 2,4-dienyl alcohols or the corresponding isomeric divinyl alcohols with bis(trifluoroethyl) malonates provide an improved method for the regio- and stereoselective dienylation of malonates. The phosphine ligand is an important control element in the reaction. Combinations of Pd(OAc)(2) with BIPHEP or BINAP give dienylated malonates in good yield and higher isomeric purity than the traditional combination of Pd(OAc)(2) and Ph3P affords in the catalyzed reactions of dienyl acetates. (C) 2003 Elsevier Ltd. All rights reserved.
• Carbon Nucleophiles in the Mitsunobu Reaction. Mono- and Dialkylation of Bis(2,2,2-trifluoroethyl) Malonates
  作者：James M. Takacs、Zhenrong Xu、Xun-tian Jiang、Alexei P. Leonov、Gregory C. Theriot

  DOI：10.1021/ol0266626

  日期：2002.10.1

  graphicSimple dialkyl malonate esters, for example diethyl malonate, exhibit relatively limited scope as carbon nucleophiles in the Mitsunobu dehydrative alkylation reaction. In contrast, bis(2,2,2-trifluoroethyl) malonate readily undergoes dehydrative alkylation with primary alcohols, and using only a slight excess of malonate gives monoalkylated product in good yield. Some secondary alcohols can also be employed, and bis(2,2,2-trifluoroethyl) malonates can be used in a second dehydrative alkylation to give dialkylated products in good to excellent yield.
• Direct Esterification of Carboxylic Acids with Perfluorinated Alcohols Mediated by XtalFluor-E
  作者：Mathilde Vandamme、Léa Bouchard、Audrey Gilbert、Massaba Keita、Jean-François Paquin

  DOI：10.1021/acs.orglett.6b03365

  日期：2016.12.16

  The direct esterification of carboxylic acids with perfluorinated alcohols mediated by XtalFluor-E is reported. The corresponding polyfluorinated esters are obtained in moderate to excellent yields with a broad range of carboxylic acids, including aromatic, heteroaromatic, aliphatic, and nonracemic chiral substrates, using only a slight excess (2 equiv) of the perfluorinated alcohol. Control experiments

  据报道，由XtalFluor-E介导的羧酸与全氟化醇直接酯化。仅使用稍微过量的（2当量）全氟化醇，就可以以中等到极高的收率，用宽范围的羧酸（包括芳族，杂芳族，脂族和非外消旋手性底物）获得相应的多氟化酯。对照实验表明，该反应不通过的酰基氟化物的形成继续进行，但最有可能通过一个（二乙基氨基）二氟- λ 4硫烷基羧酸盐中间体。